Butadiene-alkylbenzene-olefin condensation products and method for their production



Patented July 15, 1952 UNITED STAT ES g10FFlCEz" I j BUTADIENE-ALKYLBENZENE oLEFiN 'CON- 1 1 DENSATION PRODUCTS AND METHOD"FOR,'- THEIRPRODUCTIONY 1 I Daniel E. Strain, Wilmington; 15.51.; assig iiorto E. I.. du Pont de Nemours and Company, Wilmington, Del., a corporation of-Delaware No Drawing. Application September.20,

Serial No. l16,84

This invention relates to modified products from 1,3-butadiene, an alkyl substituted aromatic hydrocarbon and a polymerizable organic compound and is more particularly directed'to the condensation products of 1,3-butadiene and xylene chemically combined with a polymerizable organic compound and "processes of preparing them.

Condensation products have been made from 1,3-butadiene and cyclic hydrocarbons having at bepurified byfvacuum topping t'o remove unreacted monomer and low-boiling polymers; The resulting copolymers' have many valuable inherentv properties which particularly fit them for use least one aromatic nucleus and no olefinic side chains (Hofiman et a1. U. S. Patent 1,934,123). In the copending application of DE. Strain and W. F. Gresham, S. N. 15,958, filed March 19,.

1948, are described oil like products which are produced by condensing 1,3-butadiene with alkyl substituted benzenes and more especially with in the varnish, paint; lacquer and allied fields as resinous adjuvants, linseed 'oil substitutes and bodying agents; 1. 7 i The firststep of the process may be conducted in accord with-the details disclosed in the copending, application S N. l 5 ,9 5 8 supra in accord with which process"1;3-buta'diene and an alkyl substituted benzene, such, for example, as toluene,

1 ethyl benzene, diethylbenzene, triethyl benzene, propyl benzene, isopropyl benzene, secondary butyl benzenes, and highenalkyl substituted benzenes are brought together in a closed-autoxylene, there being present in the resulting product from 1 to 13 or more butadiene grbups per mole of the alkyl substituted benzene. The 'invention of this case is directed to such condensation products and related condensation products that have been chemically modified.

An object of the present invention is to provide chemically modified products from 1 ,'3 -butadiene and an alkyl substituted benzene reaction product. Another object of the invention is to provide copolymers from condensation products of 1,3-butadiene and an alkyl substituted hydrocarbon, such as benzene, with polymerizable organic compounds. Yet another object is to provide new compositions of matter comprising the reaction products of a polymerizable organic compound containing mcnoolefinic unsaturation with the condensation product of 1,3-butadiene and xylene. 'Other'objects and advantages of the invention will hereinafter appear.

The invention is particularly directed to the second step of a two-step process. In the first step, a condensation product is prepared from 1,3-butadiene and an alkyl substituted benzene. In the second step the condensation product of the first step is copolymerized with a polymerizable organic compound. The product of the first step, which may. .be produced in accord: with the process of the aforesaid Strain and Gresham application, or by any other suitable pressure between 3 and 20 atmosphere clave and in the presence of sodium or ,other alkali metal as the catalyst. The sodium isndispersed throughout the reaction mixture; finely divided form, and the mixture heated nder'a temperature ranging between 75 and 225 der these conditions a condensation between the 1,3-butadiene and the alkyl substituted benzene occurs, the catalyst is removed by neutralization with z'asuit'able organic acid such as acetic or br opio'ni'c acid or washed fromthe reaction product with water and the condensation product separated from the unconverted-reactants 'bydistillation.

The product of the firststepis then subjected to copolymerization with" a 'polymerizable; organic compound, this copolymerization being conducted in the presence orabsence of a polymerization catalyst under; a temperature between 60 and 250 0.. Generally nocatalystisrequired, the

. rcopolymerization reactionbeing ,conductedv by heating the mixture of; the l,3-butadiene-alkyl monomeric, cfimlpoilnd containing a polymerizasubstituted benzene ,with the monomeric poly- -40.

merizable -organic ,compound at a temperature between 150 and 200 C. Alternatively, the

. 2 0B atal st is -added over a period of time-tothe condensationproduct while maintaining the .re-

action mixture at polymerization; temperatures.

. The-polymerization .is allowed to proceed until the desired degree ofqmodification'of the condensation producti'is attainedQ-Valuable productsare produced by continuing ;.the. polymerization to a or'higheri The 1,3-butadiene alkyl substituted .aromatic' hydrocarbon may be'prepared .b or any other suitable process:' I F 'viscosi'tybetween 4000 and 200,000 op; at=25.";C.

this

Equaliiweightslofabutadiene and ma *or other a1ky1"si1bstituted hydrocarbon is reacted con- .the' reflux condenser.

tinuouslyin the presence of 1% (based on bu tadiene) of finely-dispersed sodium at 100C. and

has been removed by water washing the synthesis product is flashed at mm.and a temperature of about 170 C; for the xylene removal. The flasher distillate is redistilled in a Fenske column molecular weight oils. Three flat cuts above xylene may be obtained. illustrative of therefinedproducts obtainableirom the crude buta diene-xylene oil are the four products listed in Table I. Sample A is a purified cut which com I sists' principally of dimers resulting from the addition of one mole of butadiene to one mole of 250 p..s. i. pressure. After the sodium. catalyst V to remove unreacted xylene and pure cuts of low 7 .Inallmaterial details the process of Example 1 --Was followed in producing the copolymer of this example. The charge was heated at 134 to 145 xylene (O-, m p-xylene and ethyl benzene; sam- H ple B similarly illustrates trimers, sample Ct tetramers of respectively 2:1 and 3:1, moles of 'butadiene per mole of xylene. Sample D. consists of a mixture of reaction products averaging between 5 and 7 moles of 'butadiene per mole of xylene. 'Iodine number (standard Wijs procedure) ,.refractive index; specific gravityand other pertinent properties of the products are shown; The theoretical iodine'number and the theoreti cal molecular weight values are calculated on the basis of a butadiene-xylene addition product.

TABLE I 7 Relic-tionproducts of batddiene m was 0. for 2 hoursand minutes during which all of the styren'e benzoyl peroxide mixture was added. Thetem'perature was then gradually increased to 200 C. over a period of minutes and theproduct then allowed to cool slowly. The product was a red, opalescent liquid with a viscosity of 32,000 cp. at 25 C. With the addition of 0.l6% of mixed drier a clear air dried film was formedin 16 hours having a pencil hardness of 2B The iodine number of the selectedD oil was 356 and the molecular weight Was6ll as determined byrthe boiling point procedure. Theiodine 'n'umberof the copolymer product was 280 and-the molecular'weight was 8-42. V 1

Sample Code.--- A B '0 Approx. Mole ratio butadiene xylene 1 1 2:1 3:1 Av. 5-7. Boiling range,O./mm.'Hg m 146-151/100 -150/10 p 130/1 Ap ror. boilingpoint, 760 mm-- 222 280 lod ue number, experimental. 173 239 287 320-380. 7 Theoretical iodine numbern 159 235 284 336368. Refractive Index N5" 1. 5045 1. 5092 1. 5072 cs, 1.5120 8 ecific gravity 60 F./607F-- 0. 88 0.890 0.890 ca'0.900. iscosity 01).", 25 C cal 20-1200.

Samples heat-bodied 8 hrs./300 0.: V r V Iodinenumben; V- 164 less than 50;

Refractive indenNs" 1.5302 .i greaterthan1.54. Specific gravity, 60 F./60 F 0.930 greater than 0.95.- 1 r Viscosity, cp.,.25 C 22 gels.

as they areiin the process of the first step unless otherwise indicated:

EXAMPLE. 1

. parts product D time:

90 partsbutylmethacrylate (0.63 mols) 1 part benzoyl peroxide. V

l-liter, B-neck fiask;fitted with a reflux condenser; stirrer and thermometer. The benzoyl peroxide was dissolved in thebutyl methacrylate and the solution was] added dropwise through A 7 The addition of butyl' 1 methacrylate. required approximately 2 hours and the charge wasthenallowed to cool slowly to room temperature. The product obtained was 'a 'clear, redliquid having a viscosity of 6300 on.

V The invention is illustrated by the examples :0 which follow and in which partsareby weight at 25 C. The viscosity of the original condensa'-' tion product was approximately 500 pp. at 25 C. By the addition of 0.16% mixed lead, manganese and cobalt drier this original condensation prod-, uct formed onstanding at room temperature I a'nd'in 16 hours a clear,'air dried film having a pencil hardness of 7B."

The 'butadienexylene/butylmethacrylate "copolymer with the same amount of drienai'r dried in16 hours to a clear film having a pencil hardness of 53. m

600 parts oil-D p EXAMPL -.31:

612 partsoilD of TablejI 212 parts noriyl inethacrylate- 1 mol) Y 10.9parts glycerine [(0.13 mol) V The materials listed above were charged to 'a 2- liter flaskfandheated at a temperature between 1200 and '230fC'. for 2 hours; An orange colored.

'opalescent liquid Was formed which had a .vis-

' cosity oi-9000'cp.at- 25 C. The product with 0.16% Of mixed drier driedto a film'hardness of 7B in 19 hoursandto film hardness of 2B in 40' hours. v

7 EXAMPLE 4 a "306 parts oilD fro'm'TableI r 50 parts fme'thyl V m'eth'acrylate (containing inhibitor) A Y Theymateria'ls were added to a" l -liter. flask fitted with a stirrer and reflux condenserand heatedto a temperature betweenfl48 and C. for, ab'out .7 hours during which there wasjvery litle reflux; The product was a brown. colored. o es e .l id'hav ns FV QS Y o 4 0cm).

at 25C. With 0.16% of inixeddrier this materialdriedto a pencilha'rdness' of "5B in. 241 hours. .Q", 1'1xAM LE-5ifrom Tables-I 50 parts maleic 'anhydride (045' mol) 50partstoluene;

an'acid number v I oil D was added. Thereafter the mixture'was utes.

days.

The selected oiL D from Table'I used in this example had an iodine number of 356 a molecular weight of 573 and a viscosityot 600: cp. at C. The materials were charged to a flask fitted with a reflux condenser and a stirrer. The charge was for 1 /2 hours and cooled rapidly. ,Theproduct was a light yellow colored liquid having a vis-' cosity of 35,000 cp. at 25 C. With 0.16% of mixed drierthis material gave a clear film which air dried to a pencil hardness of 7B in 16 hours.

EXAMPLE 6 600 parts oil D from Table I I 1 156 parts m-butanol (2.05 mols); 98 parts maleic anhydride (l.0mol) The butanol and maleic acid were reacted until of 64.5 was obtained and then the was 7B and after 2 /2 months 7I-I. Unmodified 011 D dries to a hardness of greater than 9H in 5 EXAMPLE 7 400 parts oil D from Table I 400 parts lauryl methacrylate (1.6 mols) The oil D of Table I used in this example had 7 an iodine number of 359, a molecular weight of 638 and a viscosity of 500 cp. at 25 C. The charge was heated at 190 to 220 C. for 3 hours. The

product had a viscosity of 30,000 cp. at 25 C. and an iodine number of 153. By the addition of 0.16% of mixed drier, an air dried film was prepared. The hardness of this film was 1H after 6 weeks and 1H after 10 weeks' EXAMPLE 8 450 parts oil D from Table I (ca. 0.8 mol) 150 parts dicyclopentadiene (1.1 mols) 'heated to a temperature between 135 and 18,4 C.

ample, as methyl, ethyl, propyl; butyl and higher aliphatic alcohol esters of methacrylic acid), acrylic acid esters '(such, for example, as'methyl. ethyl, propyl, butyl and highermolecular' weight alkylesters of acrylic acid), phe"n'ol f ormaldehyde, melamine formaldehyde, urea formaldehyde, isobutylene, isomerized rubber, coumarin 'indene resins, poly amides, and; in fact, any

aliphatic, 'aromatic or aliphatic "aromatic polymerizable organic compound containing monoolefinic unsaturation.'-' 'Diene's and other polymerizable polyunsaturated compounds, other than 1,3-butadiene j' may likewise be copolymerized with the 1,3-butadiene alkyl substituted aromatic hydrocarbon condensatio'ri' products, examples of such compounds are; isoprene,

v butene, dimethylbutadiene, andthelike'i The condensation product similar to that shown as oil D used in this example had a true iodine number of 347, a molecular weight of 557, a viscosity of 500 cp. and a refractive index value of 1.5227. The charge was refluxed at anincreasing temperature starting at 175 C. After 7 hours the temperature had reached 230 C. and refluxing had substantially stopped. The charge was then held at 230 C. for an hour and subsequently allowed to cool. The product had a viscosity of 32,000 cp. and the refractive index was 1.5372. A film prepared from this material and 0.16% of mixed metal driers air dried in 18 hours to a pencil hardness of 4H.

Pencil hardness is the hardest lead which on applying at a pressure sufllcient to crumble the lead does not scratch the film.

Not only can the condensation product, of the first step be copolymerized with the organic compounds described in the examples but also these condensation products of the first step may be copolymerized with vinyl acetals, vinyl chloride, vinylidene chloride, vinyl alcohol, styrene, vinyl acetate, methacrylic acid esters (such, for ex- Generally speaking the f copolymerization' reaction may be conducted at temperatures between 50 and 300C. and-preferably at temperatures between and 200 C. I Pressures may be used if desired although the reaction is preferably conducted at atmospheric pressures.

The ratio of condensation pro'ducts to the polymerizable unsaturated organic compounds may be varied through wide limits, excellent products, however, being prepared with from 0.1'to 10 parts by weight of the condensation product per part of the polymerizable organic compound.

Catalysts generally are employed to speed up the polymerization reaction, although the reaction will go without a catalyst, and. for this purpose peroxygen catalysts are recommended such, for example, as benzoyl peroxide, trichloroacetyl peroxide, diisopropyl dicarbonate, the dialkyl peroxides such as dimethyl, diethyl, dipropyl and the higher dialkyl peroxides as well as the azo catalysts and particularly those that contain acyclic azo -N:N- such as are described in the Hunt, Patent 2,471,959 of May 31, 1949.

The examples illustrate the preparation of copolymers particularly with "selected oil D products of Table I. Similar products having a wide range of properties can be prepared from 1,3- butadiene-xylene condensation products having the proportion of 1,3-butadiene to xylene of oils A, B or C of Table I or from the oils produced by the process of the Strain et al. disclosure having other ranges for these reactants and from the other condensation products of 1,3-butadiene and other alkyl substituted aromatic hydrocarbons of those inventors.

The products produced in accord with the process of this application may be used in varnish, paint, lacquer, and coating compositions generally, as well as in the production of inks, core oils, linoleum and the like, the copolymers being compounded in a manner similar to linseed oil and like drying oils, and may likewise be used the presence of an alkali metal.

2. A process for the preparation of a copolymer of claim 1 which comprises heating together, in the presence of a polymerization catap 3. Acopolymer of apolyn ierizabieorganic coinpound :of, the group consisting of. mono and diolefinic-unsaturated compounds; other than 1,3- .Vbutadiene," and a 1,3-butadienexy1e ne condensatiori product, the condensation product. having been prepared by heating. 1,3-butadiene with xyle znein the presence of; sodium. g 4. Ac0po1ymer of methyl'rnethacrylate and a butadiene with xylene in thepresence of sodium. 7 6. A copolymer of maleic anhydride and a 1,3- butadiene-xyl ene condensation product, the condensati on product having been prepared by heat ing 1,3-butadienewith xylene in the presence of sodium. V v

7. A copolymer of dicyclopentadiene-and a 1,3- Q

butadiene-xylene condensation. product, the. condensation product having beenprepared by heateing 1,3-butadiene ith xylene in the-Presence, sodium.

s. A co olymer Osman. m -same and a 1,3-butadienexylene' condensation product, the

1,3-butadiene-xy1ene condensation product, the condensation product having-been prepared by heating-IB-butadiene with xylene in the presence Jofsodium.--' l i '5. Acopolymer of styrene anda 1,3-butadienei ,xylene condensationproduct, the condensation product having been prepared by heating 1,3-

condensation product having been prepared by heating 1,3-butadiene with xylenein the presenceofsodium.-

' I I p DnNIEL E. STRAIN.

REFERENCES: CITED The following referencesare of record in the fileof thispatentrf I J5 1 UNITED sTATEsfPATENTs Number V Name. ?Date 7 2,234,204 Starkweather et al. J. Mart-n, 1941 2,279,293 Clifford 'Apr. 4,1942

I B GN; TEN I Numberv Country v p Date 333,872" Great Britain Aug.-15,- 1930 .Oct.- 9, 1941 

4. A COPOLYMER OF METHYLMETHACRYLATE ANDA 1,3-BUTADIENE-XYLENE CONDENSATION PRODUCT, THE CONDENSATION PRODUCT HAVING BEEN PREPARED BY HEATING 1,3-BUTADIENE WITH XYLENE IN THE PRESENCE OF SODIUM. 